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WO2012171998A1 - Polyesters ramifiés contenant des groupes sulfonate - Google Patents

Polyesters ramifiés contenant des groupes sulfonate Download PDF

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Publication number
WO2012171998A1
WO2012171998A1 PCT/EP2012/061291 EP2012061291W WO2012171998A1 WO 2012171998 A1 WO2012171998 A1 WO 2012171998A1 EP 2012061291 W EP2012061291 W EP 2012061291W WO 2012171998 A1 WO2012171998 A1 WO 2012171998A1
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WO
WIPO (PCT)
Prior art keywords
acid
diol
branched polyesters
component
functional
Prior art date
Application number
PCT/EP2012/061291
Other languages
German (de)
English (en)
Inventor
Monika Haberecht
Jürgen Detering
Bernd Bruchmann
Helmut Witteler
Heike Weber
Karl Kolter
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to ES12728477.6T priority Critical patent/ES2555872T3/es
Priority to JP2014515189A priority patent/JP6038130B2/ja
Priority to RU2014100963/04A priority patent/RU2014100963A/ru
Priority to EP12728477.6A priority patent/EP2721090B1/fr
Priority to KR1020147001009A priority patent/KR20140053098A/ko
Priority to CN201280028898.2A priority patent/CN103608379B/zh
Priority to BR112013031119A priority patent/BR112013031119A2/pt
Priority to CA2836532A priority patent/CA2836532A1/fr
Priority to MX2013014810A priority patent/MX341198B/es
Publication of WO2012171998A1 publication Critical patent/WO2012171998A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6888—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Definitions

  • the present invention relates to branched polyesters with sulfonate groups and mixtures containing branched polyesters with sulfonate groups.
  • the invention further provides a process for preparing such branched polyesters.
  • the invention furthermore relates to the use of these branched polyesters as coating inhibitors in water-carrying systems and as an additive to dishwashing, washing and cleaning agents, in particular to phosphate-containing and phosphate-free detergent formulations for machine dishwashing.
  • branched copolyesters containing sulfonate groups are known from DE 26 21 653 A1. These branched copolyesters are suitable, according to DE 26 21 653 A1, as leveling agents in polyester dyeing, especially for fast dyeing processes, as hair setting agents, as sizes, as water-soluble adhesives and as additives for adhesives, and as modifiers for melamine resins or other aminoplast resins.
  • DE 26 33 418 A1 describes hair treatment compositions containing water-soluble or dispersible branched copolyesters containing sulfonate groups.
  • DE 26 37 926 A1 water-soluble or dispersible and branched copolyesters containing sulfonate groups are described with a comparable to DE 26 21 653 A1 range of applications.
  • US Pat. No. 5,281,630 describes a prepolymer based on a terephthalic polymer, glycol and oxyalkylated polyol which is reacted with ⁇ , ⁇ -unsaturated dicarboxylic acids and subsequently sulfonated.
  • Alemdar et al. describe in Polymer 51 (2010), pp 5044-5050 the production of unsaturated polyesters using boric acid as a catalyst and sulfonated derivatives of unsaturated polyester as biodegradable polymeric surfactants.
  • DE 39 05 915 A1 relates to a coating composition containing addition polymers, crosslinking agents and an acid catalyst.
  • hydroxyl-containing succinic diester sulfonic acids and succinic acid polyester sulfonic acids are described.
  • Simple sulfosuccinates for example mono- or dialkyl sulfosuccinates or sulfosuccinamides, have been familiar to the person skilled in the art since as early as 1930. These sulfosuccinates are used, for example, in cleaning agents, pharmaceuticals, adhesives or coatings. However, polymeric sulfosuccinates are rarely used.
  • Copolymers of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid are frequently used for this purpose. These polymers are also used in water-bearing systems as a means of preventing mineral deposits such as calcium and magnesium sulfate, magnesium hydroxide, calcium and barium sulfate and calcium phosphate on heat transfer surfaces or in pipes use. As water-bearing systems here u.a. Refrigeration and boiler feedwater systems and industrial process waters. But also in seawater desalination by distillation and membrane processes such as reverse osmosis or electrodialysis these polymers are used as scale inhibitors.
  • the object of the invention was therefore to provide substances which can be used for cleaning purposes, in particular as an additive to phosphate-containing and phosphate-free detergent formulations for machine dishwashing, and for the purpose of inhibiting coating in water-bearing systems and are readily biodegradable.
  • the invention was further based on the object by means of a technically simple and inexpensive process to provide polymeric effect substances that have a high number of carboxy groups and / or sulfonic acid groups, and consist of low toxicity and good biodegradability monomers.
  • Another object of the invention was to provide substances that are easy to incorporate into formulations for cleaning purposes in their various dosage forms.
  • the component A is selected from the group of ⁇ , ⁇ -olefinically unsaturated dicarboxylic acids (A2), and
  • the component B is selected from the group of di- or higher-functional alcohols (By),
  • the optional component C is selected from the group of di- or higher-functional carboxylic acids (A x ) and hydroxycarboxylic acids (A x B y ) without ⁇ , ⁇ -olefinically unsaturated bonds,
  • the optional component D is selected from the compounds of the formula CHs (-O-CH 2 -CH 2) n -OH, where n corresponds to an integer from the range from 2 to 40,
  • component B2 if only difunctional alcohols (B2) are selected as component B, the component C in the reaction (a.) Is present and from the group of tri- or higher functional carboxylic acids (A x ) and the tri- or higher - Functional hydroxycarboxylic acids (A x B y ) is selected without ⁇ , ⁇ -olefinic unsaturated bonds, b. and the subsequent reaction of the branched polyesters obtained in (a.) with hydrogen sulfite, wherein the molar amount of hydrogen sulfite is at most 95 mol%, based on the amount of ⁇ , ⁇ -olefinically unsaturated dicarboxylic acid (A2).
  • mixtures of different components A, mixtures of different components B, optional mixtures of different components C and / or optionally mixtures of different components D can be used in the reaction of components A, B, optionally C and D optionally to branched polyesters.
  • a compound A, B and optionally C are used in the reaction of components A, B, optionally C and optionally D to branched polyesters.
  • the carboxylic acids (A x ) of component C carry no sulfonic acid or sulfonate groups.
  • the branched polyesters with sulfonate groups of the invention are preferably dendritic, in particular hyperbranched, polyesters.
  • dendritic polymer or hyperbranched polymer is the generic term for a number of different branched molecular structures. These include, for example, dendrimers, star polymers and hyperbranched polymers.
  • Dendrimers arise from a center (i.c., a small molecule with multiple reactive end groups) attached to it by a repetitive, controlled reaction sequence, generation by generation, of a branching monomer. Thus, with each reaction step, the number of monomer end groups in the resulting dendrimer increases exponentially.
  • a characteristic feature of dendrimers is the number of reaction stages (generations) performed to build them up. Due to their uniform structure (ideally, all branches contain exactly the same number of monomer units), dendrimers are essentially monodisperse, i. H. they usually have a defined molecular weight. Molecular as well as structurally uniform hyperbranched polymers are also referred to below uniformly as dendrimers.
  • Hyperbranched polymers in the context of this invention are highly branched polymers which, in contrast to the abovementioned dendrimers, are both molecularly and structurally nonuniform. Hyper-weakened polymers therefore have a nonuniform molecular weight distribution (polydispersity).
  • polydispersity polydispersity
  • Dendritic polymers can be characterized by their branching degree "Degree of Branching.” For the definition of the degree of branching, see H. Frey et al., Acta Polym., 1997, 48, 30.
  • L is the average number of linearly bound monomer units.
  • Dendrimers generally have a degree of branching DB of at least 99%, especially 99.9 to 100%.
  • Hyperbranched polymers preferably have a degree of branching DB of 10 to 95%, preferably 25 to 90% and in particular 30 to 80%.
  • the branched polyesters used according to the invention preferably have a degree of branching (DB) per molecule of from 10 to 95%, preferably from 10 to 90%, particularly preferably from 10 to 80%, and in particular from 20 to 80%.
  • DB degree of branching
  • Hyperbranched polyesters with or without sulfonate groups are understood in the context of this invention to mean uncrosslinked polyesters with or without sulfonate groups, which are structurally as well as molecularly nonuniform.
  • Uncrosslinked in the context of this document means that a degree of crosslinking of less than 15% by weight, preferably less than 10% by weight, determined by the insoluble fraction of the polymer, is present.
  • the insoluble fraction of the polymer was determined by extraction for 4 hours in a Soxhlet apparatus with a solvent in which the polymer is soluble, for example tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol, preferably tetrahydrofuran. After drying the residue to constant weight, a weighing of the remaining residue.
  • the branched polyesters according to the invention having sulfonate groups are obtained using component D, with preferably less than 20 mol% of component D based on the total amount Components A, B, C and D are used. More preferably, less than 10 mol% of component D are used here.
  • the component D is preferably selected from the compounds of the formula CH 3 (-O-CH 2 -CH 2) n -OH, where n is an integer from the range from 2 to 30, particularly preferably from 2 to 25.
  • step a in step a. the proportion of the trifunctional or higher-functional components B and / or C in admixture with the difunctional components B and / or C of from 50 to 100 mol%, preferably from 70 to 100 mol% and very particularly preferably from 80 to 100 mol% %, based on the total amount of components B and / or C.
  • step a in step a. the proportion of tri- or higher-functional components B and / or C at least 30 mol% based on the total amount of components A, B, C and D, more preferably at least 35 mol% and most preferably at least 40 mol%.
  • step a at least 30 mol% of components B and, if present, trifunctional or higher functional, based on the total amount of components A, B, C and D. Preference is given here to at least 35 mol%, particularly preferably 40 mol% and in particular at least 45 mole% of components B and, if present, C tri- or higher functional.
  • the proportion of tri- or higher-functional components B and, if present, C, based on the total amount of components A, B, C and D, is preferably at most 90 mol%, preferably at most 80 mol%, very preferably at most 75 mol%.
  • step a in step a. at least 5 mol% of components A, based on the total amount of components A, B, C and D. Preferably, at least 10 mol% are used here. Preferably, the proportion of component A, based on the total amount of components A, B, C and D is at most 50 mol%, preferably at most 40 mol%.
  • the amount of hydrogen sulfite in step b. may vary within the scope of the branched polyester according to the invention with sulfonate depending on the particular application in a wide range.
  • the weight-average molecular weights (M w ) of the polyester A thus determined before the reaction with hydrogen sulfite are in the range from 500 g / mol to 50,000 g / mol, preferably in the range from 750 g / mol to 25,000 g / mol and most preferably in the range from 1000 g / mol to 15,000 g / mol.
  • the branched polyesters before the reaction with hydrogen sulfite have acid numbers of 10 to 500 mg KOH / g polymer, preferably 15 to 400 mg KOH / g polymer and very particularly preferably 20 to 300 mg KOH / g polymer.
  • the determination of the acid number was carried out in accordance with DIN 53402.
  • the branched polyesters A prior to the reaction with hydrogen sulfite have glass transition temperatures in the range of -50 to +50 ° C, preferably -40 to +40 ° C and most preferably -30 to +40 ° C.
  • the determination of the glass transition temperature is carried out by means of DSC (Differential Scanning Calorimetry).
  • ⁇ , ⁇ -olefinically unsaturated dicarboxylic acids are preferably maleic acid, itaconic acid, fumaric acid, citraconic acid, mesaconic acid or glutaconic acid. Particular preference is given to maleic acid and itaconic acid, most preferably maleic acid and its derivatives, such as maleic anhydride.
  • the dicarboxylic acids (A2) can be used either as such or in the form of derivatives.
  • Mono- or dialkyl esters preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters,
  • mixed esters preferably mixed esters with different C1-C4 alkyl components, more preferably mixed methyl ethyl esters.
  • Ci-C4-alkyl in this document means methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, particularly preferably methyl and ethyl, and most preferably methyl.
  • Polyethylene glycols HO (CH 2 CH 2 O) n -H or polypropylene glycols HO (CH [CH 3 ] CH 2 O) n -H, where n is an integer and n> 4, preferably n is an integer from the range from 4 to 40, more preferably from 4 to 20, polyethylene-polypropylene glycols, wherein the sequence of the ethylene oxide of the propylene oxide units may be blockwise or random, or polytetramethylene glycols, poly-1,3-propanediols or polycaprolactones having a molecular weight of up to 5000 g / mol, preferably used with a molecular weight of up to 2000 g / mol.
  • difunctional alcohols B 2
  • branched polyesters with sulfonate groups tri- or higher-functional alcohols (By with y equal to 3 or higher) are preferred.
  • Glycerine trimethylolmethane, trimethylolethane, trimethylolpropane
  • TEEIC Tris (hydroxyethyl) isocyanurate
  • Sugars or sugar alcohols such as glucose, fructose or sucrose, sugar alcohols such as e.g. Sorbitol, mannitol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol, isomalt, or inositol, tri- or higher functional polyetherols based on trifunctional or higher alcohols, which are converted by reaction with ethylene oxide , Propylene oxide and / or butylene oxide are obtained or tri- or higher functional polyesterols based on tri- or higher functional alcohols, which are obtained by reaction with caprolactone used.
  • sugar alcohols such as glucose, fructose or sucrose
  • sugar alcohols such as e.g. Sorbitol, mannitol, threitol, erythritol, adonite (ribi
  • Glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane are particularly preferred as tri- or higher-functional alcohols (By with y equal to 3 or higher),
  • Di trimethylolpropane
  • pentaerythritol sucrose or sorbitol
  • polyetherols based on ethylene oxide and / or propylene oxide and in particular
  • Glycerol diglycerol, triglycerol, trimethylolethane, trimethylolpropane, pentaerythritol or their polyetherols based on ethylene oxide used.
  • Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane are preferred for the branched polyesters having sulfonate groups as di- or higher functional carboxylic acids (Ax) without ⁇ , ⁇ -olefinically unsaturated bonds - ⁇ , ⁇ -dicarboxylic acid, dodecane- ⁇ , oo-dicarboxylic acid, cis- and trans -cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-
  • Trimellitic acid and its derivatives for example their anhydrides and / or ester derivatives, or pyromellitic acid and its derivatives, for example their anhydrides and / or ester derivatives are used.
  • the di- or higher-functional carboxylic acids (Ax) can be used either as such or in the form of derivatives.
  • Derivatives are preferably understood to mean the relevant anhydrides in monomeric or else polymeric form, Mono- or dialkyl esters, preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters,
  • mixed esters preferably mixed esters with different C1-C4 alkyl components, more preferably mixed methyl ethyl esters.
  • anhydrides and the mono- or dialkyl esters preference is given to the anhydrides and the mono- or dialkyl esters; the anhydrides and the mono- or di-C 1 -C 4 -alkyl esters are particularly preferred, and the anhydrides are very particularly preferred.
  • branched polyesters having sulfonate groups as di or higher functional carboxylic acids (Ax) without ⁇ , ⁇ -olefinic unsaturated bonds are aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane- ⁇ , ⁇ -dicarboxylic acid, dodecane-a, oo-dicarboxylic acid, dodecenylsuccinic acid, hexadecenylsuccinic acid or Octadecenylbernsteinklad.
  • aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane- ⁇ , ⁇ -dicarboxylic
  • Citric acid the hydrates of citric acid, such as citric acid monohydrate, hydroxyacetic acid, hydroxypropionic acid, hydroxyvaleric acid, malic acid, tartaric acid, isocitric acid, are preferred for the branched polyesters with sulfonate groups as hydroxycarboxylic acids (A x B y ) without .alpha.,. Beta.-olefinically unsaturated bonds , Dimethylolpropionchure or Dimethylolbutterklad.
  • the branched polyesters with sulfonate groups are based on a number of different components A, B and C, the small is ner or equal to 4, ie in step a. 4 or less different components A, B and C are used.
  • the number of different components A, B and C is 3.
  • the number of different components A, B and C is at least 2.
  • the amount of component A is greater than 20 mol%, preferably greater than 30 mol%, particularly preferably greater than 50 mol%, based on the total amount of carboxylic acids of components A and C together.
  • Another embodiment of the invention is given by mixtures of the branched polyesters according to the invention with sulfonate groups.
  • Such mixtures contain, in addition to the branched polyesters of the invention, other ingredients such as solvents or surfactants.
  • branched polyesters of the invention may be incorporated directly into the formulations (blends) in their various dosage forms by methods known to those skilled in the art.
  • solid formulations such as powders, tablets and liquid formulations should be mentioned.
  • Another object of the invention is therefore the use of the branched polyester according to the invention with sulfonate groups or mixtures thereof in detergents, cleaners or detergents, in particular in dishwashing detergents.
  • they can be used in automatic dishwashing detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, they inhibit deposits of calcium and magnesium carbonate and calcium and magnesium phosphates and phosphonates. In addition, they prevent deposits that come from the dirt components of the rinse, such as fat, protein and starch coverings.
  • the mechanical cleaning formulations according to the invention can be provided in liquid or solid form, single- or multi-phase, as tablets or in the form of other dosing units, packaged or unpackaged.
  • the polymers can be used both in multi-component product systems (separate use of detergent, rinse aid and regenerating salt) and in dishwashing detergents in which the functions of detergent, rinse aid and regenerating salt are combined in one product (3-in-1 products, 6 -in-1 products, 9-in-1 products, all in one products).
  • a preferred embodiment of the mixtures according to the invention is given by a cleaning formulation for machine dishwashing containing as components: a) 1 to 20 wt .-% of at least one polymer of the invention
  • bleaching agent 0.1 to 30% by weight of bleaching agent and optionally bleach activators
  • enzymes 0 to 8% by weight of enzymes, h) 0 to 50% by weight of one or more further additives, such as anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tablet thickening agents Disintegrating agent, thickener, solubilizer and water, the sum of components a) to h) being 100% by weight.
  • further additives such as anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tablet thickening agents Disintegrating agent, thickener, solubilizer and water, the sum of components a) to h) being 100% by weight.
  • Components b) to h) are known to the person skilled in the art from the prior art and are described generally in WO 2008/13213 A1 and in DE 2007 006630 A1.
  • Suitable complexing agents b) are described, for example, in WO 2008/13213 A1 p.24-26.
  • phosphates c) for example, the substances described in WO 2008/13213 A1 p. 18-21 are used.
  • builder and co-builder d) are meant, for example, the substances described in WO 2008/13213 A1 p. 21-24 and in DE 2007 006630 A1 p. 5-7.
  • Suitable nonionic surfactants e) can be found by the person skilled in the art, for example, in DE 2007 006630 A1 p. 9-12.
  • Bleaching agents and bleach activators f) are familiar to the person skilled in the art, for example, from WO 2008/13213 A1 p. 29-31.
  • Examples of enzymes g) are described in WO 2008/13213 A1 p.26-29.
  • the proportions of the individual components are set by the skilled person depending on the particular application of the cleaning formulation.
  • Another object of the invention is the use of branched polyesters according to the invention with sulfonate groups or mixtures thereof as scale inhibitors in water-bearing systems. Water-bearing systems in which the polymers of the invention can be used are in particular seawater desalination plants, cooling water systems and boiler feedwater systems and industrial process waters.
  • the polymers according to the invention are added to the water-conducting systems in amounts of from 0.1 mg / l to 100 mg / l.
  • the optimum dosage depends on the requirements of the particular application or on the operating conditions of the respective process.
  • the polymers are preferably used in concentrations of 0.5 mg / l to 10 mg / l.
  • polymer concentrations of up to 100 mg / l are used.
  • water analyzes are carried out to determine the proportion of scale-forming salts and thus the optimal dosage.
  • water-conducting systems formulations which, in addition to the polymers according to the invention, may also be added as required.
  • Phosphonates, polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors such as benzotriazole, tolyltriazole, benzimidazole or Ethinylcarbinolalkoxylate, biocides, complexing agents and / or surfactants may contain.
  • phosphonates are 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBTC), aminotrimethylenephosphonic acid (ATMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and ethylenediaminetetra (methylenephosphonic acid). (EDTMP), which are each used in acid form or in the form of their sodium salts,
  • Another object of the invention is a process for the preparation of branched polyesters with sulfonate groups, comprising
  • the component A is selected from the group of ⁇ , ⁇ -olefinically unsaturated dicarboxylic acids (A2), and
  • the component B is selected from the group of di- or higher-functional alcohols (By),
  • the optional component C is selected from the group of di- or higher-functional carboxylic acids (A x ) and hydroxycarboxylic acids (A x B y ) without ⁇ , ⁇ -olefinically unsaturated bonds
  • the optional component D is selected from the compounds of the formula CHs (-O-CH 2 -CH 2) n -OH, where n corresponds to an integer from the range from 2 to 40,
  • component B2 if only difunctional alcohols (B2) are selected as component B, component C is present in the reaction (a.) and is selected from the group of tri- or higher-functional carboxylic acids (A x ) and hydroxycarboxylic acids (A x B y ) is chosen without ⁇ , ⁇ -olefinically unsaturated bonds,
  • Step 1 The process according to the invention can be carried out in bulk or in the presence of a solvent.
  • Suitable solvents are, for example, hydrocarbons such as paraffins or aromatics.
  • paraffins are n-heptane and cyclohexane.
  • aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene.
  • ethers such as, for example, dioxane or tetrahydrofuran and ketones, for example methyl ethyl ketone and methyl isobutyl ketone.
  • the amount of solvent added is according to the invention at least 0.1% by weight, based on the mass of the starting materials to be reacted, preferably at least 1 wt .-% and particularly preferably at least 10 wt .-%. It is also possible to use excesses of solvent, based on the mass of reacted starting materials to be reacted, for example 1:01 to 10 times. Solvent amounts of more than 100 times, based on the mass of reacted starting materials to be reacted, are not advantageous because significantly lower concentrations of the reactants, the reaction rate decreases significantly, resulting in uneconomical long reaction times.
  • reaction is carried out free of solvent.
  • step 1 in the process according to the invention it is possible to work as an additive in the presence of a dehydrating agent which is added at the beginning of the reaction.
  • a dehydrating agent which is added at the beginning of the reaction.
  • Suitable examples are molecular sieves, in particular molecular sieve 4A, MgSC and Na 2 SO 4 .
  • acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, sulfates and hydrogen sulfates, such as sodium hydrogensulfate, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH ⁇ 6, in particular ⁇ 5) and acidic aluminum oxide.
  • aluminum compounds of the general formula AI (OR 1 ) 3 and titanates of the general formula Ti (OR 1 ) 4 can be used as acidic inorganic catalysts, wherein the radicals R 1 may be the same or different and are independently selected from each other
  • C 1 -C 20 -alkyl radicals for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n -Decyl, n-dodecyl, n-hexadecyl or n-octadecyl.
  • C 3 -C 12 -cycloalkyl radicals for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
  • radicals R 1 in Al (OR 1 ) 3 or Ti (OR 1 ) 4 are preferably identical and selected from n-butyl, isopropyl, 2-ethylhexyl, n-octyl, decyl or dodecyl.
  • Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R 1 2 SnO or Dialkylzinndiestern R 1 2 Sn (OR 2) 2 wherein R 1 is as defined above standing and can be identical or different.
  • R 2 may have the same meanings as R 1 and additionally C 6 -C 12 aryl, for example phenyl, o-, m- or p-tolyl, xylyl or naphthyl. Each R 2 may be the same or different.
  • organotin catalysts examples include tin (II) n-octanoate, tin (II) 2-ethylhexanoate, tin (II) laurate, dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate. Also conceivable are antimony, bismuth or organoaluminium catalysts.
  • acidic organometallic catalysts are dibutyltin oxide, diphenyltin oxide and dibutyltin dilaurate.
  • Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups.
  • Particularly preferred are sulfonic acids such as para-toluene sulfonic acid.
  • acidic ion exchangers as acidic organic catalysts, for example polystyrene resins containing sulfonic acid groups, which are crosslinked with about 2 mol% of divinylbenzene.
  • acidic inorganic, organometallic or organic catalysts preference is given to using from 1 to 10,000 ppm of catalyst, more preferably from 2 to 5,000 ppm, based on the total mass of the hydroxy- and carbo- xy-containing compounds.
  • the process according to the invention is carried out at temperatures of 60 to 140.degree.
  • enzymes are, for example, selected from hydrolases
  • esterases EC 3.1 .-
  • lipases EC 3.1.1.3
  • glycosylases EC 3.2 .-
  • proteases EC 3.4. -.- in free or on a support chemically or physically immobilized form, preferably lipases, esterases or proteases and particularly preferably esterases (EC 3.1.-.-).
  • Novozyme 435 lipase from Candida antarctica B
  • the enzymes listed are commercially available, for example from Novozymes Biotech Inc., Denmark.
  • the enzyme content in the reaction medium is generally in the range of about 0.1 to 10 wt .-%, based on the sum of the components used
  • step 1 the method according to the invention at temperatures of 20 and to 120 ° C, preferably 20 to 100 ° C and particularly preferably 20 to 80 ° C.
  • the reaction is carried out at temperatures of 60 to 140.degree. Preferably, one works at temperatures of 80 to 130 ° C.
  • the process according to the invention is preferably carried out under an inert gas atmosphere, i. a gas which is inert under the reaction conditions, for example under carbon dioxide, combustion gases, nitrogen or noble gas, of which in particular argon can be mentioned.
  • an inert gas atmosphere i. a gas which is inert under the reaction conditions, for example under carbon dioxide, combustion gases, nitrogen or noble gas, of which in particular argon can be mentioned.
  • the pressure conditions of the process according to the invention are generally not critical. You can work at significantly reduced pressure, for example at 10 to 500 mbar. The process according to the invention can also be carried out at pressures above 500 mbar. For reasons of simplicity, the reaction is preferably at atmospheric pressure; but it is also possible to carry out at slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly elevated pressure, for example, at pressures up to 10 bar. Preferably, the reaction is at reduced or atmospheric pressure, more preferably at atmospheric pressure.
  • the reaction time of the process according to the invention is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours and particularly preferably 1 to 12 hours.
  • the highly functional branched polyester can be easily isolated, for example by filtering off the catalyst and optionally removing the solvent, wherein the removal of the solvent is usually carried out at reduced pressure. Further suitable work-up methods are precipitation of the polymer after addition of water and subsequent washing and drying.
  • the reaction mixture may be discolored, for example by treatment with activated carbon or metal oxides, such as alumina, silica, Magnesium oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for example, 0.1 to 50 wt .-%, preferably 0.5 to 25 wt .-%, particularly preferably 1 to 10 wt .-% at temperatures of for example 10 to 140 ° C, preferably 20 to 130 ° C and more preferably 30 to 120 ° C are subjected.
  • activated carbon or metal oxides such as alumina, silica, Magnesium oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for example, 0.1 to 50 wt .-%, preferably 0.5 to 25 wt .-%, particularly preferably 1 to 10 wt .-% at temperatures of for example 10 to 140 ° C, preferably 20 to 130 ° C and more preferably 30 to 120 ° C are subjected.
  • the decolorization of the reaction mixture can be carried out at any point in the work-up procedure, for example at the stage of the crude reaction mixture or after any pre-wash, neutralization, washing or solvent removal.
  • the reaction mixture can furthermore be subjected to prewashing and / or neutralization and / or after-washing, preferably only to neutralization.
  • neutralization and pre-wash can also be reversed in the order.
  • the desired products of value can be at least partially recovered by acidification and extraction with a solvent and used again.
  • all extraction and washing processes and apparatuses known per se can be used, e.g. those described in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed, 1999 Electronic Release, Chapter: Liquid - Liquid Extraction - Apparatus.
  • these can be one-stage or multistage, preferably single-stage extractions, and those in cocurrent or countercurrent mode, preferably countercurrent mode.
  • Step 2 of the process according to the invention for the sulfonation of the polyesters can be carried out in bulk or in the presence of a solvent.
  • Suitable solvents are, for example, water or alcohols.
  • the amount of solvent added is according to the invention at least 0.1% by weight, based on the mass of the starting materials to be reacted, preferably at least 1 wt .-% and particularly preferably at least 10 wt .-%. It is also possible to use excesses of solvent, based on the mass of reacted starting materials to be reacted, for example 1:01 to 10 times. Solvent amounts of more than 100 times, based on the mass of reacted starting materials to be reacted, are not advantageous because significantly lower concentrations of the reactants, the reaction rate decreases significantly, resulting in uneconomical long reaction times.
  • Step 2 of the process according to the invention is carried out at temperatures of 60 to 150 ° C.
  • the polyester is preferably initially introduced at the reaction temperature as a stirrable melt and then mixed with an aqueous solution of the sulfonating reagent.
  • sulfonating reagent solutions of the alkali or alkaline earth salts of the sulfurous acid (hydrogen sulfites) can be used.
  • concentration of the solutions is from 10 to 90% by weight, preferably from 20 to 50% by weight and most preferably from 30 to 45% by weight.
  • Preference is given to using aqueous solutions of sodium, potassium or magnesium hydrogen sulfite. Very particularly preferred aqueous solutions of sodium hydrogensulfilt.
  • an acidic aqueous solution of sodium thiosulfate may be used which disproportionates into hydrogen sulfite.
  • the reaction time in step 2 of the process according to the invention is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours and particularly preferably 1 to 3 hours.
  • the reaction is complete when no more hydrogen sulfite can be detected in the reaction mixture.
  • the consumption of hydrogen sulfite in the reaction mixture can be monitored qualitatively or quantitatively.
  • qualitative tracking for example, the treatment of a sample of the reaction mixture with dilute potassium permanganate solution and subsequent addition of barium chloride solution is suitable.
  • Existing hydrogen sulfite is first oxidized by permanganate to sulfate which precipitates on contact with barium ions as sparingly soluble barium sulfate. It should be noted that the detection can be disturbed by reaction of the potassium permanganate with maleic acid double bonds.
  • the present invention provides branched Polyesters with sulfonate groups which, due to the high density of carboxylic acids, carboxylates and / or sulfonates, can be used for cleaning purposes and for the purpose of water treatment and yet are readily biodegradable. are produced by means of a technically relatively simple and inexpensive process and can be easily incorporated into formulations for cleaning purposes in their various dosage forms.
  • TMP trimethylolpropane
  • TMP x n EO reaction product of TMP with n molar excess of ethylene oxide
  • ASA octadecenyl succinic acid
  • x% NaHS03 means that the amount of NaHSO3 required to sulfonate x% of the ⁇ , ⁇ -olefinically unsaturated double bonds theoretically present in the polymer was used in the sulfonation reaction.
  • the molecular weights of the unsulfonated polyesters were determined by gel permeation chromatography (GPC) (column combination: 2 ⁇ PLgel 3 ⁇ MIXED-E and 1 ⁇ ResiPore 3 ⁇ ; standard: polymethylmethacrylate (PMMA); eluent: THF).
  • the acid numbers (mg KOH / g polymer) were determined according to DIN 53402.
  • the product was obtained in the form of a yellow water-soluble resin.
  • the product was obtained in the form of a yellow water-soluble resin.
  • the product was obtained in the form of a yellowish water-insoluble resin.
  • the product was obtained as a yellow water-soluble and waxy solid.
  • Sulfonated polymer 3a (ZS: MSA: TMP) * 30% NaHSOs:
  • the product was obtained as a yellow water-soluble and waxy solid.
  • a solution of NaHCO 3, Mg 2 SO 4, CaC and polymer is shaken for 2 h at 70 ° C in a water bath.
  • the Ca content of the filtrate is determined complexometrically or by means of a Ca 2+ -selective electrode and by comparing before / after the CaCO 3 inhibition in% determined (see formula I).
  • the polymers were tested in the following phosphate-free formulations PF1 and PF2, as well as in the phosphate-based formulation P1.
  • the composition of the polymers is given in Table 3 (in% by weight).
  • Dishwashing detergent 21 g
  • Rinse cycles 15; between each 1 h break (10 min open door, 50 min closed door)
  • the washware was evaluated after 15 cycles in a darkened chamber under light behind a pinhole.
  • Starch 0.5% potato starch, 2.5% gravy
  • the formulations with polymer are characterized in particular by their very high deposit-inhibiting action against inorganic and organic deposits on glass, knives, porcelain and plastic parts. Furthermore, they increase the cleaning power of the dishwashing detergent and promote the drainage of the water from the items to be washed, so that particularly clear glasses and shiny metal cutlery are obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des polyesters ramifiés contenant des groupes sulfonate, pouvant être obtenus par réaction des composants A, B, éventuellement C et éventuellement D pour former des polyesters ramifiés, le composant A étant choisi dans le groupe constitué par les acides dicarboxyliques à insaturation α,β-oléfinique, et le composant B étant choisi dans le groupe constitué par les alcools difonctionnels ou de fonctionnalité supérieure, le composant C éventuel étant choisi dans le groupe constitué par les acides carboxyliques ou les acides hydroxycarboxyliques difonctionnels ou de fonctionnalité supérieure sans liaisons à insaturation α,β-oléfinique, le composant D éventuel étant choisi parmi les composés de formule CH3(-O-CH2-CH2)n-OH, à la condition que si le composant B est choisi uniquement parmi les alcools difonctionnels, le composant C est présent lors de la réaction et est choisi dans le groupe constitué par les acides carboxyliques trifonctionnels ou de fonctionnalité supérieure et les acides hydroxycarboxyliques trifonctionnels ou de fonctionnalité supérieure sans liaisons à insaturation α,β-oléfinique, les polyesters ramifiés ainsi obtenus étant ensuite mis en réaction avec de l'hydrogénosulfite, la quantité molaire d'hydrogénosulfite étant inférieure ou égale à 95 % en moles, par rapport à la quantité d'acide dicarboxylique à insaturation α,β-oléfinique.
PCT/EP2012/061291 2011-06-15 2012-06-14 Polyesters ramifiés contenant des groupes sulfonate WO2012171998A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
ES12728477.6T ES2555872T3 (es) 2011-06-15 2012-06-14 Poliésteres ramificados con grupos sulfonato
JP2014515189A JP6038130B2 (ja) 2011-06-15 2012-06-14 スルホネート基を有する分岐状ポリエステル
RU2014100963/04A RU2014100963A (ru) 2011-06-15 2012-06-14 Разветвленные сложные полиэфиры с сульфонатными группами
EP12728477.6A EP2721090B1 (fr) 2011-06-15 2012-06-14 Polyesters ramifiés contenant des groupes sulfonate
KR1020147001009A KR20140053098A (ko) 2011-06-15 2012-06-14 술포네이트 기를 갖는 분지형 폴리에스테르
CN201280028898.2A CN103608379B (zh) 2011-06-15 2012-06-14 具有磺酸盐基团的支化聚酯
BR112013031119A BR112013031119A2 (pt) 2011-06-15 2012-06-14 poliéster ramificado, mistura, uso dos poliésteres ramificados, e, método para produzir poliésteres ramificados
CA2836532A CA2836532A1 (fr) 2011-06-15 2012-06-14 Polyesters ramifies contenant des groupes sulfonate
MX2013014810A MX341198B (es) 2011-06-15 2012-06-14 Poliesteres ramificados con grupos sulfonato.

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EP11170063.9 2011-06-15

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
JP2014522444A (ja) * 2011-06-15 2014-09-04 ビーエーエスエフ ソシエタス・ヨーロピア スルホネート基を有する分岐状ポリエステル
US9382377B2 (en) 2011-08-10 2016-07-05 Basf Se Polymer mixtures as deposit inhibitors in water-bearing systems
DE102017003927A1 (de) * 2016-12-05 2018-06-07 Gertraud Scholz Anionische Soll Release Polyester und deren Verwendung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3050950B1 (fr) * 2015-02-02 2018-09-19 The Procter and Gamble Company Nouvelle utilisation de polymères sulfonés
WO2024096665A1 (fr) * 2022-11-04 2024-05-10 주식회사 엘지화학 Polymère de poly(acide 3-hydroxypropionique) ramifié

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DE2633418A1 (de) 1976-07-24 1978-01-26 Hoechst Ag Haarbehandlungsmittel
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JP2014522444A (ja) * 2011-06-15 2014-09-04 ビーエーエスエフ ソシエタス・ヨーロピア スルホネート基を有する分岐状ポリエステル
US9382377B2 (en) 2011-08-10 2016-07-05 Basf Se Polymer mixtures as deposit inhibitors in water-bearing systems
DE102017003927A1 (de) * 2016-12-05 2018-06-07 Gertraud Scholz Anionische Soll Release Polyester und deren Verwendung

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MX341198B (es) 2016-08-11
JP2014518291A (ja) 2014-07-28
JP6038130B2 (ja) 2016-12-07
RU2014100963A (ru) 2015-07-20
EP2721090A1 (fr) 2014-04-23
EP2721090B1 (fr) 2015-09-09
MX2013014810A (es) 2014-01-24
ES2555872T3 (es) 2016-01-11
CA2836532A1 (fr) 2012-12-20
CN103608379B (zh) 2015-08-05
KR20140053098A (ko) 2014-05-07
BR112013031119A2 (pt) 2016-12-06

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